Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/08—Homopolymers or copolymers of acrylic acid esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/005—Repairing damaged coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/56—Three layers or more
  • B05D7/57—Three layers or more the last layer being a clear coat
  • B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
  • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
  • C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2202/00—Metallic substrate
  • B05D2202/10—Metallic substrate based on Fe
  • B05D2202/15—Stainless steel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies

Definitions

• the present invention relates generally to coating compositions, and substrates coated with such compositions, as well as to a method for repairing such coated substrates v
• coatings processes include the application of several different coating layers onto an automobile body.
• coating layers can include for example, an electrodeposition primer layer, a sealer layer, a basecoat layer, and a ciearcoat layer.
• the coating compositions used to form each of these coating layers may be waterborne or solventbome compositions or in solid particulate form. Due to recent government VOC regulations, one or more of these coating layers typically is formed from waterborne coating compositions.
• Each of these original layers may require a thermal bake at a relatively high temperature to achieve complete cure of the coating. For example, an original ciearcoat layer may be cured at a temperature within the range.
• the bake temperature of one or more of the coating layers applied during this repair process may be lower than that used to cure the original layer.
• a repair clearcoat layer may be capable of curing at temperatures, such as within the range of 160 0 F to 180 0 F (71 0 C to 82°C), in order to achieve complete cure.
• a coating composition which is useful as both an original and a repair finish, contains low or no VOC or HAP (i.e. Hazardous Air Pollutant) materials, and provides improved water resistance properties demonstrated by improved blistering resistance and improved adhesion between the coating layers. . .
• VOC or HAP i.e. Hazardous Air Pollutant
• the present invention is directed to a coating composition
• a coating composition comprising:
• a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprising:
• . ' at least.20 weight percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or a . monomer having a functional group capable of reacting to form crosslinks after polymerization; .
• (b) at least 2 weight percent of a polymerizable ethylenically unsaturated monomers having hydrophilic functional groups, the monomer having the following structure (I) or (II):
• A represents H or C 1 -C 3 alkyl
• B represents - NR 1 R 2 , -OR 3 or -SR 4 , where R 1 and R 2 are independently H, C 1 -C 18 alkyl, C 1 - C 18 alkylol or C 1 -C 18 alkylamino
• R 3 and R 4 are independently C 1 -C 18 alkylol, C 1 -C 18 alkylamino, -CH 2 CH 2 -(OCH 2 CH 2 ) H -OH where n is O to 30, or , - CH 2 CH 2 -(OC(CH 3 )HCH 2 ) m -OH where m is 0 to 30
• D represents H or C 1 -C 3 alkyl
• E represents -CH 2 CHOHCH 2 OH, C 1 -C 18 alkylol, -CH 2 CH 2 - (OCH 2 CH 2 ) n -OH where n is 0 to 30, or -CH 2 CH 2
• (c) optionally, the balance comprised of a polymerizable ethylenically unsaturated monomer, wherein (a), (b) and (c) are different from each other; and
• thermosetting composition comprising: . . .
• A represents H or C 1 -C 3 alkyl
• B represents - NR 1 R 2 , -OR 3 or -SR 4 , where R 1 and R 2 are independently H, C 1 -Ci 8 alkyl, Cr G 18 alkylol or C-I-Ci 8 alkylamino, R 3 and R 4 are independently Ct-Ci 8 alkylol, Ci-Cis alkylamino, -GH 2 CH 2 -(OCH 2 CH 2 )n-OH where n is Q to .
• the present invention is directed to a method of repairing a defect in a multi-layer coating comprising applying the coating composition of the present invention.
• any numerical range recited herein is intended to include all sub-ranges subsumed therein.
• a range of "1 to 10" is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
• the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.
• thermosetting composition is meant one which "sets" irreversibly upon curing or crosslinking, wherein the polymer chains of the polymeric components are joined together by covalent bonds. This property is usually associated with a crosslinking reaction of the composition constituents often induced, for example, by heat or radiation. Hawley, Gessner G., The Condensed Chemical Dictionary, Ninth Edition., page 856; Surface Coatings, Vol. 2, Oil and Colour Chemists' Association, Australia, TAFE Educational Books (1974). Curing or crosslinking reactions also may be carried out under ambient conditions.
• thermosetting composition Once cured or crosslinked, a thermosetting composition will not melt upon the application of heat and is insoluble in solvents.
• a thermoplastic composition comprises polymeric components which are not joined by covalent bonds and thereby can undergo liquid flow upon heating and are soluble in solvents. Saunders, K.J., Organic Polymer Chemistry, pp. 41-42, Chapman and Hall, London (1973).
• the term “polymer” is meant to encompass prepolymers, oligomers, and includes without limitation both homopolymers and copolymers.
• the term “reactive” refers to a functional group that forms a covalent bond with another functional group under conditions sufficient to cure the composition.
• the term “capable of reacting” with regard to a functional group refers to the capability of a functional group to form a covalent bond with another functional group.
• the term “polyisocyanate”, unless otherwise indicated, is intended to include blocked (or capped) isocyanates as well as unblocked (poly)isocyanates.
• the term "glass transition temperature” refers to the temperature at which an amorphous material, such as glass or a high polymer, changes from a brittle vitreous state to a plastic state.
• the glass transition temperature is theoretically calculated according to the equation described on page 29 in The Chemistry of Organic Film Former by D. H. Solomon, Wiley and Sons, 1967.
• the term “cure” as used in connection with a composition e.g., “composition when cured,” shall mean that any crosslinkable components of the composition are at least partially crosslinked.
• the crosslink density of the crosslinkable components i.e., the degree of crosslinking, ranges from 5% to 100% of complete crosslinking.
• the present invention is directed to a coating composition
• a coating composition comprising:
• a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprising:
• A represents H or CrC 3 alkyl
• B represents - NR 1 R 2 , -OR 3 or -SR 4 , where R 1 and R 2 are independently H, C 1 -Ci 8 alkyl, Ci- C- 18 alkylol or C 1 -Ci 8 alkylamino, R 3 and R 4 are independently C 1 -Ci 8 alkylol, C 1 -Ci 8 alkylamino, -CH 2 CH2-(OCH 2 CH 2 )n-OH where n is 0 to 30, or , - CH 2 CH 2 -(OC(CH 3 )HCH 2 )m-OH where m is 0 to 30; D represents H or Ci-C 3 alkyl; and E represents -CH 2 CHOHCH 2 OH, C 1 -C 18 alkylol, -CH 2 CH 2 - (OCH 2 CHz) n -OH where n is 0 to 30, or -CH 2 CH 2 -(OC(CH 3 )
• (c) optionally, the balance comprised of a polymerizable ethylenically unsaturated monomer, wherein (a), (b) and (c) are different from each other; and
• (iii) optionally, a polymerizable ethylenically unsaturated monomer, wherein (i), (ii) and (iii) are different from each other; and wherein the polymer has a glass transition temperature of no more than -10 0 C.
• alkylol is meant a hydrocarbon radical that contains one or more hydroxyl groups.
• alkylamino is meant a hydrocarbon radical that contains one or more amine groups.
• (meth)acrylic acid and like terms are intended to include acrylic acid and/or methacrylic acid.
• a "suitable” material is a material that may be used in or in preparing the latex emulsion that includes crosslinked polymeric microparticles dispersed in an aqueous continuous phase, so long as the material does not substantially affect the stability of the latex emulsion or the polymerization process.
• Crosslinking monomers suitable for use as the crosslinking monomer (a) of latex emulsion (I) can include any monomer having two or more sites of reactive unsaturation, or any monomer that has a functional group capable of reacting to form crosslinks after polymerization.
• functional groups that are capable of reacting to form crosslinks after polymerization refer to functional groups on a first polymer molecule that may react under appropriate conditions to form covalent bonds with functional groups on a second polymer molecule to form a crosslinked polymer.
• Functional groups that may react to form crosslinks include, but are not limited to N-alkoxymethyl amides, N-methyloIamides, lactones, lactams, mercaptans, hydroxyls, epoxides and the like.
• the crosslinking monomer can have two sites of reactive unsaturation.
• the crosslinking monomer may
• - a- comprise ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate., 1 ,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1 ,1 ,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1 ,1 ,1-
• the crosslinking monomer (a) comprises at least 15 weight percent, or at least 20 weight percent, or at least 22.5 weight percent, or at least 25 weight percent of the monomer mix used to prepare the polymeric microparticles. Also, the crosslinking monomer comprises not more than 45 weight percent, or not more than 40 weight percent, or not more than 35 weight percent, or not more than 30 weight percent of the monomer mix used to prepare the polymeric microparticles.
• the level of the crosslinking monomer (a) used is determined by the desired properties that are to be incorporated into the resulting microparticle.
• the crosslinking monomer may be present in the monomer mix at any value or in any combination of the recited ranges inclusive of those values stated above.
• any polymerizable ethylenically unsaturated monomers having hydrophilic functional groups can be used as the monomer (b).
• polymerizable ethylenically unsaturated monomers having hydrophilic functional groups described by structures I and/or Il above may be used as the monomer (b) provided that the monomer can be polymerized in a latex emulsion polymerization system and does not substantially affect the stability of the latex emulsion or the polymerization process.
• Polymerizable ethylenically unsaturated monomers having hydrophilic functional groups suitable for use as the monomer (b) in the preparation of the polymeric microparticles of the present invention include, but are not limited to (meth)acrylamide, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl (meth)acrylate, allyl glycerol ether, methallyl glycerol ether and/or polyethyleneoxide allyl ether.
• a particular advantage of the present crosslinked polymeric microparticles is that they do not require the presence of an alkaline material to swell the microparticles, thereby providing desired rheological properties. This eliminates the additional processing step of adding an alkaline material to promote particle swelling and renders the resulting rheological properties more predictable.
• the polymerizable ethylenically unsaturated monomers having hydrophilic functional groups (b) include monomers described by structure (I) above.
• the polymerizable ethylenically unsaturated monomers having hydrophilic functional groups (b) include monomers described by structure (II) above.
• the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises at least 2 weight percent, or greater than 2 weight percent, or at least 5 weight percent, or greater than 5 weight percent, or at least 7 weight percent, or at least 8 weight percent of the monomer mix used to prepare the polymeric microparticles.
• the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups comprises not more than 35 weight percent, or not more than 30 weight percent, or not more than 20 weight percent, or not more than 15 weight percent of the monomer mix used to prepare the polymeric microparticles.
• the level of the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups used is determined by the properties that are to be incorporated into the resulting microparticle.
• the level of the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups present in the monomer mix can range between any combination of the recited values inclusive of the recited values.
• Polymerizable ethylenically unsaturated monomers suitable for use as the monomer (c) which, optionally, make up the remainder of the monomer mix, and which are different from the crosslinking monomer (a) and the monomer having hydrophilic functional groups (b), may be included in the polymeric microparticles of the present invention.
• Any suitable polymerizable ethylenically unsaturated monomer may be used, provided that it is capable of being polymerized in a latex emulsion polymerization system and does not substantially affect the stability of the latex emulsion or the polymerization process.
• Suitable polymerizable ethylenically unsaturated monomers include, but are not limited to, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2- ethylhexyl(meth)acrylate, isobomyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and/or 3,3,5-trimethylcyclohexyl (meth)acrylate.
• the polymerizable ethylenically unsaturated monomer (c) may comprise at least 20 weight percent, or at least 30 weight percent, or at least 40 weight percent, or at least 50 weight percent of the monomer mix used to prepare the polymeric microparticles.
• the polymerizable ethylenically unsaturated monomers may comprise not more than 80 weight percent, or not more than 75 weight percent, or not more than 70.5 weight percent, or not more than 67 weight percent of the monomer mix used to prepare the polymeric microparticles.
• the level of the polymerizable ethylenically unsaturated monomer (c) which can be used is determined by the properties that are to be incorporated into the resulting microparticle.
• the level of the polymerizable ethylenically unsaturated monomer (c) present in the monomer mix may range between any combination of the recited values inclusive of the recited values.
• the crosslinking monomer (a) comprises glycol di(meth)acrylates and/or glycol tri(meth)acrylates;
• the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises (meth)acrylamide;
• the polymerizable ethylenically unsaturated monomer (c) comprises an alkyl(meth)acrylate.
• the latex emulsion (I) of crosslinked polymeric microparticles dispersed in an aqueous continuous phase is prepared by latex emulsion polymerization of (a), (b) and optionally, (c) as described above.
• the monomer mixture of (a), (b) and (c) will readily disperse into stable monomer droplets and micelles as would be expected in a Smith-Ewart type of process.
• no monomeric or polymeric emulsifiers and/or protective colloids are added to the latex emulsion, and the latex emulsion is substantially free of polymeric emulsifiers and/or protective colloids.
• a surface active agent may be added to the aqueous continuous phase to stabilize, or prevent coagulation or agglomeration of the monomer droplets, especially during polymerization.
• a surface active agent can be present in the latex emulsion of the present invention at any level that stabilizes the emulsion.
• the surface active agent may be present at least 0.001 percent by weight, or at least 0.005 percent by weight, or at least 0.01 percent by weight, or at least 0.05 percent by weight based on the total weight of the latex emulsion.
• the surface active agent may be present at not more than 10 percent by weight, or not more than 7.5 percent by weight, or not more than 5 percent by weight, or not more than 3 percent by weight based on the total weight of the latex emulsion.
• the level of the surface active agent used is determined by the amount required to stabilize the latex emulsion.
• the surface active agent may be present in the latex emulsion at any level or in any range of levels inclusive of those stated above.
• the surface active agent may be an anionic, cationic, or nonionic surfactant or dispersing agent, or compatible mixtures thereof, such as a mixture of an anionic and a nonionic surfactant.
• surfactants and dispersing agents are well known in the art, any of a variety of which may be suitable. .
• a free radical initiator typically is used in the latex emulsion polymerization process. Any suitable free radical initiator as are well known in the art may be used: Suitable, free radical initiators include, but are not limited to thermal initiators, photoinitiators and oxidation-reduction initiators, all of which may be otherwise categorized as being water-soluble initiators or non- water-soluble initiators.
• the average particle size of the polymeric microparticles may be at least 0.001 microns, or at least 0.005 microns, or at least 0.01 , or at least 0.02 microns.
• the average particle size of the polymeric microparticles typically is not more than I micron, or not more than 0.9 microns or not more than 0.8 microns.
• the average particle : size of the polymeric microparticles may be any value or in any range of values inclusive of those stated above
• the latex emulsion of crossl inked polymeric microparticles dispersed in an aqueous continuous phase is prepared by a seeded latex emulsion polymerization process.
• a seeded latex emulsion polymerization process includes:
• step (III) polymerizing the remainder of monomers (a), (b) and (c) in the presence of the dispersed polymeric seeds prepared in step (II) to form a latex emulsion of seeded polymeric microparticles.
• the coating composition also comprises a polymer (II) comprising (i) a Cs to C2 0 alkyl ester of (meth)acrylic acid; (ii) a polymerizable ethylenically unsaturated monomer comprising a polar functional group; and (iii) optionally, a polymerizable ethylenically unsaturated monomer, wherein (i), (ii) and (iii) are different from each other; and wherein the polymer has a glass transition temperature of no more than -10 0 C.
• a polymer (II) comprising (i) a Cs to C2 0 alkyl ester of (meth)acrylic acid; (ii) a polymerizable ethylenically unsaturated monomer comprising a polar functional group; and (iii) optionally, a polymerizable ethylenically unsaturated monomer, wherein (i), (ii) and (iii
• the Cs to C 2 o afkyl ester of (meth)acrylic acid (i) of polymer (II) can comprise, for example, octyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, and/or eicosyl (meth)acrylate.
• the Cs to C 20 alkyl ester of (meth)acrylic acid comprises lauryl (meth)acrylate.
• the C 8 to C 2 o alkyl ester of (meth)acrylic acid used to prepare polymer (II) may be present at an amount of at least 50 weight percent and not more than 99.9 weight percent based on total weight of monomer solids.
• the C 8 to C 2 o alkyl ester of (meth)acrylic acid may comprise at least 50 weight percent, or at least 70 weight percent, or at least 90 weight percent based on the total weight of monomer solids used to prepare polymer (II).
• the C 8 to C 2 o alkyl ester of (meth)acrylic acid may comprise not more than 99.9 weight percent, or not more than 95 weight percent, or not more than 85 weight percent based on the total weight of monomer solids used to prepare polymer (II).
• the level of the C 8 to C 20 alkyl ester of (meth)acrylic acid which can be used is determined by the properties that are to be incorporated into the resulting polymer (II).
• the level of the C 8 to C 2 o alkyl ester of (meth)acrylic acid present in the monomer mix may range between any combination of the recited values inclusive of the recited values.
• polymer (II) comprises a polymerizable ethylenically unsaturated monomer comprising a polar functional group.
• polar functional group refers to a functional group having a high dielectric constant and strong polarity. Any suitable polymerizable ethylenically unsaturated monomer having a polar functional group can be used.
• the polar functional group can comprise, for example, carboxyl groups, hydroxyl groups, and/or amine groups.
• the polar functional group comprises a carboxyl group.
• the ethylenically unsaturated monomer (ii) of polymer (II) comprises (meth)acrylic acid.
• the ethylenically unsaturated monomer (ii) used to prepare polymer (II) is present at an amount of at least 0.1 weight percent and not more than 5 weight percent based on total weight of monomer solids.
• the ethylenically unsaturated monomer (ii) may comprise at least 0.1 weight percent, or at least 1 weight percent, or at least 4 weight percent based on the total weight of monomer solids used to prepare polymer (II).
• the ethylenically unsaturated monomer (ii) also may comprise not more than 5 weight percent, or not more than 3 weight percent, or not more than 2 weight percent based on the total weight of monomer solids used to prepare polymer (II).
• the level of the ethylenically unsaturated monomer (ii) which can be used is determined by the properties that are to be incorporated into the resulting polymer (II).
• the level of the ethylenically unsaturated monomer (ii) present in the monomer mix may range between any combination of the recited values inclusive of the recited values.
• the polymer (II) optionally comprises a polymerizable ethylenically unsaturated monomer, wherein (i), (ii) and (iii) are different from each other.
• any suitable polymerizable ethylenically unsaturated monomer may be used, provided that the polymer (II) has a glass transition temperature of no more than -10 0 C.
• these polymerizable ethylenically unsaturated monomers may be present in any suitable amount provided that the glass transition temperature of polymer (II) does not exceed -10 0 C.
• polymer (II) has a glass transition temperature of no more than -3O 0 C.
• polymer (II) is present in the coating composition at an amount of at least 2 weight percent, or at least 5 wefght percent resin solids based on the total weight of resin solids of the coating composition.
• the polymer (II) may be present in the coating composition at an amount of not more than 30 weight percent, or not more than 15 weight percent resin based on the total weight of resin solids of the coating composition.
• the level of polymer (II) which can be used is determined by the properties that are to be incorporated into the resulting coating composition.
• the level of the polymer (II) present in the coating composition may range between any combination of the recited values inclusive of the recited values.
• certain embodiments of the coating compositions of the present invention further comprise an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium.
• Suitable polyurethane-acrylate particles can comprise the reaction product obtained by polymerizing the components of a pre-emulsion formed from: (A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
• (C) a crosslinking monomer; wherein the polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having a terminal polymerizable site of ethylenic unsaturation at one end of the molecule and an active hydrogen-containing group at the opposite end of the molecule; and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising a prepolymer having a terminal polymerizable site of ethylenic unsaturation at each end of the molecule.
• the active hydrogen-containing polyurethane acrylate prepolymer (A) in the polyurethane-acrylate particles is present in an amount of at least 20 percent by weight, or at least 25 percent by weight, or at least 30 percent by weight, or at least 35 percent by weight or at least 40 percent by weight of the solids of the polyurethane-acrylate particles. Further, the active hydrogen- containing polyurethane acrylate prepolymer (A) may be present in an amount of up to 80 percent by weight, or up to 75 percent by weight, or up to 70 percent by weight, or up to 65 percent by weight or up to 60 percent by weight of the solids of the polyurethane-acrylate particles.
• the level of active hydrogen-containing polyurethane acrylate prepolymer (A) in the polyurethane-acrylate particles can be any value or range between any combination of these values inclusive of the recited values.
• the hydrophobic polymerizable ethylenically unsaturated monomers (B) in the polyurethane-acrylate particles are present in an amount of at least 20 percent by weight, or at least 25 percent by weight, or at least 30 percent by weight, or at least 35 percent by weight or at least 40 percent by weight of the solids of the polyurethane-acrylate particles.
• hydrophobic polymerizable ethylenically unsaturated monomers (B) may be present in an amount of up to 80 percent by weight, or up to 75 percent by weight, or up to 70 percent by weight, or up to 65 percent by weight or up to 60 percent by weight of the solids of the polyurethane-acrylate particles.
• the level of hydrophobic polymerizable ethylenically unsaturated monomers (B) in the polyurethane-acrylate particles can be any value or range between any combination of these values inclusive of the recited values.
• the crosslinking monomer (C) in the polyurethane-acrylate particles is present in an amount of at least 1 percent by weight, or at least 2 percent by weight, or at least 3 percent by weight, or at least 4 percent by weight or at least 5 percent by weight of the solids of the polyurethane-acrylate particles. Further, the crosslinking monomer (C) may be present in an amount of up to 20 percent by weight, or up to 17.5 percent by weight, or up to 15 percent by weight, or up to 12.5 percent by weight or up to 10 percent by weight of the solids of the polyurethane-acrylate particles.
• the level of crosslinking monomer (C) in the polyurethane-acrylate particles can be any value or range between any combination of these values inclusive of the recited values.
• the value of (A) + (B) + (C) can be 100%, but will be less than 100% when other components as are known to those skilled in the art are also included in the polyurethane-acrylate particles.
• the polyol of (i) may be one or more polyols selected from a polyether polyol, a polyester polyol, an acrylic polyol, or a mixture thereof.
• the polyol is one or more polyether polyols described by structure VII: where R 1 is H or C 1 -C 5 alkyl including mixed substituents for example, n is from 1 to 200 and m is from 1 to 5.
• polyetherpolyols examples include, but are not limited to, poly(oxytetramethylene) glycols; poly(oxyethylene) glycols; poly(oxy-1 ,2-propylene) glycols; 1 ,6-hexanediol; poly(tetrahydrofuran); trimethylolpropane; sorbitol; pentaerythritol; the reaction products of ethylene glycol with a mixture of 1 ,2-propylene oxide and ethylene oxide; the reaction products obtained by the polymerization of ethylene oxide, propylene oxide and tetrahydrofuran and mixtures of polyols can be used as polyol (i).
• the polymerizable ethylenically unsaturated monomer comprising a hydroxyl group of (ii) may be one or more monomers described by structure VIII:
• R 2 represents H or C 1 -C 4 alkyl and R 3 represents selected from -(CHR 4 Jp-OH 1 -CH 2 CH 2 -(O- CH 2 -CH R 4 ) P -OH, -CH 2 -CHOH-CH 2 -O-CO- CR 5 R 6 R 7 , or -CH 2 -CHR 4 -O-CH 2 -CHOH-CH 2 -O-CO-CR 5 R 6 R r where R 4 represents H or C 1 -C 4 alkyl, R 5 , R 6 , and R 7 represent H or C 1 -C 2O linear or branched alkyl, and p is an integer from 0 to 20.
• polymerizable ethylenically unsaturated monomer comprising a hydroxyl group that mgy be used in the present invention as component (ii) include, but are not limited to, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, po ⁇ yethyleneglycol ester of (meth)acrylic acid, polypropyleneglycol ester of (meth)acrylic acid, the reaction product of (meth)acrylic acid and the glycidyl ester of versatic acid, the reaction product of hydroxyethyl(meth)acrylate and the glycidyl ester of versatic acid, and the reaction product of hydroxypropyl(meth)acrylate and the glycidyl ester of versatic acid.
• the glycidyl ester of versatic acid is available as CarduraTM Resin E-10 from Resolution Performance Products, Houston, TX. Mixtures of such hydroxy! group-containing monomers can be used.
• Nonlimiting suitable examples of the compound of (iii) may include dimethylol proprionic acid, and/or 12-hydroxy stearic acid.
• the polyisocyanate (iv) may be an aliphatic polyisocyanate, an aromatic polyisocyanate, or mixtures thereof.
• polyisocyanates that may be used as polyisocyanate (iv) include, but are not limited to, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 1 ,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, tolylene diisocyanate, 1 ,4- tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 1 ,4-cyclohexyl diisocyanate, alpha, alpha-xylylene diisocyanate, 4,4' ⁇ methylene- bis(cyclohexyl isocyanate), 1 ,2,4-benzene triisocyanate, and polymethylene polyphenyl isocyanate.
• the hydrophobic polymerizable ethylenically unsaturated monomers (B) may be any suitable hydrophobic polymerizable ethylenically unsaturated monomers.
• hydrophobic monomer is meant a monomer that is “substantially insoluble” in water.
• substantially insoluble in water what is meant is that a monomer has a solubility in distilled water of less than 6g/100g at 25 0 C determined by placing 3g of water and 0.18g of monomer in a test tube at 25°C and shaking the test tube. On visual examination, if two distinct layers form, the monomer is considered to be hydrophobic.
• the turbidity of the mixture is measured using a turbidimeter or nephelometer (for example, Hach Model 2100AN 1 Hach Company, Loveland, CO). A reading of greater than 10 nephelometric turbidity units (NTU) indicates that the monomer is considered to be hydrophobic.
• a turbidimeter or nephelometer for example, Hach Model 2100AN 1 Hach Company, Loveland, CO.
• NTU nephelometric turbidity units
• hydrophobic monomers include, but are not limited to, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate,.t-butyl(meth)acrylate, 2- ethylhexyl(meth)acryjate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, N- butoxy methyl (meth)acrylamide, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
• the crosslinking monomer (C) has two or more sites of polymerizable ethylenic unsaturation. Any suitable crosslinking monomer may be used to prepare the polyurethane-acrylate particles of the present aqueous polyurethane dispersion.
• suitable crosslinking monomers include, but are not limited to, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)aerylate, tetraethylene glycol di(meth)acrylate, 1 ,3-b ⁇ tylene ; glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(r ⁇ eth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acryjate, 1 ,1 ,1-tris(hydroxym
• ethyl)ethane di(meth)acrylate 1 ,1 ,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1 ,1,1- tris(hydroxymethyl)propane di(meth)acrylate, 1 ,1 ,1- tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide. Mixtures of such crosslinking monomers also can be used. [00 .
• the incorporation of the various components of the active hydrogen-containing polyurethane acrylate prepolymer can occur in a statistically predictable manner.
• an excess of hydroxy! functionality, from compounds (i), (ii) and (iii) is present relative to isocyanate functionality from the polyisocyanate of (iv).
• the distribution .and amount of the carboxylic group of the compound of (iii) on the. resulting polyurethane acrylate prepolymer determines the hydrophobic-hydrophilic balance of the prepolymer. . .
• a statistical distribution of three types of prepolymer molecules can result from the preparation of the polyurethane acrylate prepolymer.
• One type of prepolymer that can be formed is a first surfactant-like prepolymer, which has a hydroxyl and/or carboxylic functional group at one end of the prepolymer and a polymerizable ethylenically unsaturated group at the opposite end of the prepolymer.
• a second surfactant-like prepolymer can result; which has a hydroxyl and/or carboxylic functional group at both ends of the prepolymer.
• Another type of prepolymer that can ⁇ result is a hydrophobic prepolymer that does not contain any earboxylic acid groups, which has polymerizable ethylenically unsaturated groups at both ends of the prepolymer molecule.
• reaction product (A) is considered to be a mixture of the aforementioned three types of prepolymers as well as any unreacted portions of components (i), (ii), (iii) and (iv) and any reaction by-products.
• thermosetting composition comprising:
• thermosetting composition may be in any suitable physical form, for example in liquid form, such as a solution, dispersion or emulsions, and in solid form, for example, a dry, particulate powder.
• thermosetting composition is a coating composition.
• the first reactant (I) can include any suitable reactive functional groups.
• the functional groups can comprise one or more of epoxy, carboxylic acid, hydroxy, amide, oxazoline, aceto acetate, isocyanate, methylol, amino, methylol ether, and carbamate.
• the functional groups of the curing agent (II) can include any suitable reactive functional groups, provided such groups are reactive with those of the first reactant (I).
• the functional groups of the curing agent (II) can comprise one or more of epoxy, carboxylic acid, hydroxy, isocyanate, capped isocyanate, amine, methylol, methylol ether, and beta-hydroxyalkylamide.
• the functional groups of (I) and (II) will be different from and reactive with each other.
• the first reactant (I) which are suitable for use in the thermosetting compositions of the present invention include, but are not limited to, film-forming polymers with at least one reactive functional group such as those discussed immediately above with respect to the first reactant (I).
• Such polymers can include any of a variety of functional polymers known in the art. For example, suitable hydroxy!
• group-containing polymers can include acrylic polyols, polyester polyols, polyurethane polyols, polyether polyols, and mixtures thereof.
• suitable film-forming polymers with at least one functional group include those described in U.S. Application Serial No. 10/126,903 filed April 19, 2002, entitled “Coating Compositions Containing Polyurethane Dispersions And Highly Crosslinked Polymer Particles,” which is hereby incorporated by reference.
• appropriate mixtures of film-forming polymers may be used as the first reactant (I).
• thermosetting composition of the present invention further includes a curing agent (II) having functional groups reactive with the functional groups of the first reactant (I).
• the curing agent (II) can be selected from an aminoplast resin, a polyisocyanate, a blocked isocyanate, a polyepoxide, a polyacid, an anhydride, an amine, a polyol, a carboxylic acid, an hydroxy containing compound, a methylol containing compound, a methylol ether containing compound, a beta-hydroxyalkylamide, and mixtures of any of the foregoing.
• Examples of curing agents suitable for use in the compositions of the present invention are described in U.S. Application Ser. No. 10/126,903, filed April 19, 2002, entitled "Coating Compositions Containing Polyurethane Dispersions And Highly Crosslinked Polymer Particles," which is hereby incorporated by reference.
• the latex emulsion of crosslinked microparticles (III) has functional groups reactive with the functional groups of the curing agent (II).
• the latex emulsion (III) can include any suitable reactive functional groups, provided such groups are reactive with those of the curing agent.(ll). -
• thermosetting compositions can be formulated as a one-component composition where a curing agent such as an amihoplast resin and/or a blocked isocyanate compound such as those described above is admixed with other composition components.
• the ⁇ ne-component composition can be storage stable as formulated.
• the thermosetting composition can be formulated as a two-component composition where a polyisocyanate curing agent such as those described above can be added to a pre-formed admixture of the other composition components just prior.to application.
• the pre-formed admixture can comprise
• curing agents such as aminoplast resins and/or blocked isocyanate I compounds such as those described above.
• first reactant (I) and curing agent (II) suitable for use in the present compositions depends on the curing conditions of the coating as well as desired properties of the cured coating.
• thermosetting composition comprises the following components:
• thermosetting coating composition is a basecoat composition that may include one or more effect pigments.
• thermosetting coating composition can provide improved flake orientation of metallic or micaceous pigments, resulting in improved coating appearance and enhanced Flop Index ratings as described below.
• the level of effect pigments present in the thermosetting composition of the present invention can vary dependent upon the other composition components, the desired color, and/or the end use of substrate to be coated.
• the basecoat compositions can contain nonmetallic color and/or filler pigments conventionally used in surface coatings such as, for example, inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, and carbon black; and organic pigments such as phthalocyanine blue and phthalocyanine green.
• Optional ingredients in the basecoat composition can comprise those which are well known in the art of formulating surface coatings, and can comprise surface active agents, flow control agents, thixotropic agents, fillers, anti-gassing agents, organic co-solvents, catalysts, and other customary adjuvants. Nonlimiting examples of these materials and suitable amounts are described in U.S. Patent Nos. 4,220,679; 4,403,003; 4,147,769; and 5,071 ,904.
• the thermosetting composition further comprises an aqueous polyurethane dispersion in addition to components (I), (II), (III) and (IV).
• aqueous polyurethane dispersion for improving smoothness, flow and leveling of the coating film is known in the art.
• Any suitable polyurethane dispersion may be used in the present thermosetting composition.
• suitable polyurethane dispersions include, but are not limited to, those disclosed in U.S. Patent No. 5,071 , 9U4 to Martin et ai. (col. 4, line 40 to col. 9, line 8); U.S. Patent No. 6,291 ,564 to Faler et al. (col.
• the polyurethane dispersion is present in the thermosetting coating composition of the present invention in an amount sufficient to provide a smooth cured coating as measured using a Byk Gardner wave scan instrument. See https://bvk- qardnerusa.com/ritml/Bvk/references/Applications/Application 4/application 4.h.
• the shortwave values correlate to the surface smoothness of a basecoat in a basecoat/clearcoat system.
• Another embodiment of the present invention is directed to a coated substrate comprising:
• the substrate can comprise any of a variety of known substrates such as metallic, polymeric, elastomeric, glass, wood, paper and other cellulosic substrates.
• the substrate comprises a metallic substrate.
• the coating composition can be applied to the substrate by any conventional coating technique such as brushing, rolling, spraying, dipping, or flowing.
• Spray techniques and equipment for air spraying, airless spray, and electrostatic spraying in either manual or automatic methods known in the art can be used.
• the film thickness of the coating formed on the substrate can range from 0.1 to 5 mils (2.54 to 127 micrometers). In another embodiment, the film thickness of the coating formed on the substrate can range 0.1 to 1 mils (2.54 to 25.4 micrometers), and can be 0.4 to 0.6 mils (10.2 to 15.2 micrometers).
• the coated substrate can be heated to a temperature and for a time sufficient to effect cure of the thermosetting composition applied thereto.
• the composition is cured at ambient conditions.
• Another embodiment of the present invention is directed to a method of repairing a defect in a multi-layer coating comprising:
• a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprising:
• A represents H or Ci-C 3 alkyl
• B represents - NR 1 R 2 , -OR 3 or -SR 4 , where R 1 and R 2 are independently H, C 1 -C 18 alkyl, C 1 - Ci8 alkylol or C1-C18 alkylamino
• R 3 and R 4 are independently C 1 -C 18 alkylol, C 1 -Ci 8 alkylamino, -CH 2 CH 2 -(OCH 2 CH 2 ) O -OH where n is 0 to 30, or ,. - CH 2 CH 2 -(OC(CH 3 )HCH 2 ) HI -OH where m is 0 to 30, D represents.
• E represents -CH 2 CHOHCH 2 OH, C 1 -C 18 alkylol, -CH 2 CH 2 - (OCH 2 CH 2 )n-OH where n is 0 to 30, or -CH 2 CH 2 -(OC(CH 3 )HCH 2 ) m -OH where m is O to 30; and
• (c) optionally, the balance comprised of a polymerizable ethylenically unsaturated monomer, wherein (a), (b) and (c) are different from each other; and :
• (iii) optionally, a polymerizable ethylenically unsaturated monomer, wherein (i), (ii) and (iii) are different from each other; wherein the polymer has a glass transition temperature of no more than -10°C; . • . : -- .
• (B) optionally, heating the first, base coating layer at a : temperature within the range of 160 0 F to 180 0 F;
• (G) optionally, heating the coated substrate of (F) at a temperature within the range of 160°F to 180 0 F; (H) applying a second topcoat composition over at least a portion of the second base coating layer to form a second topcoat layer thereover; and
• the first base coating composition may include a pigmented basecoat composition.
• the first base coating layer can be fully cured or alternatively given a drying step in which solvent is driven out of the film by heating or an air drying period before application of the second coating layer. Suitable drying conditions may depend on the particular coating composition, and on the ambient humidity, but a drying time from 1 to 15 minutes at a temperature within the range of 70°F to 200°F (21 °C to 93°C), or within the range of 160°F to 180 0 F (71 0 C to 82°C), can be adequate.
• the first topcoat layer which may include a substantially pigment- free (or clear) coating composition, can be applied to the first base coating layer by any conventional coating technique as described above, including, but not limited to, compressed air spraying, electrostatic spraying, and either manual or automatic methods.
• the first topcoat layer can be applied directly to the first base coating layer prior to drying or curing thereof; or to a dried first base coating layer, or to a cured first base coating layer.
• the two coatings can be heated to cure both coating layers simultaneously, i.e. to form a cured multi-layer coating.
• Typical curing temperatures are within the range of 5O 0 F to 475°F (1O 0 C to 246°C), or within the range of 250 0 F to 300 0 F (121 0 C to 149°C) for 1 to 30 minutes.
• the thickness (dry film thickness) of the first topcoat layer can range from 1 to 6 mils (25 to 150 micrometers).
• the defect may be removed by any suitable method, such as by sanding, followed by re- application of one or more coating layers, the first and second base coating layers can be deposited from any of the coating compositions of the present ⁇ invention.
• the first and second base coating compositions can be the same or different.
• Suitable drying conditions may depend on the particular coating composition, and on the ambient humidity, but a drying time from 1 to 15 minutes at a temperature within the range of 70 0 F to 200°F (21 0 C to 93°C), or within the range of 16O 0 F to 180 0 F (71 0 C to 82°C), can be adequate.
• the first and second topcoat layers may be formed from the same or different topcoat composition.
• a second topcoat layer may be applied over at least a portion of the second base coating layer and, optionally, over any of the previously applied layers. In one embodiment, the second topcoat layer is different from the first topcoat layer.
• the second topcoat layer can be applied directly to the second base coating layer prior to drying or curing thereof; or to a dried second base coating layer, or to a cured second base coating layer.
• the two coatings can be heated to cure both coating layers simultaneously, i.e. to form a cured multi-layer coating.
• the second topcoat layer may be heated at a temperature within the range of 180 0 F to 200 0 F (82°C to 93°C) for 30 to 45 minutes to effect cure.
• the second topcoat layer can be cured at room temperature.
• the thickness (dry film thickness) of the second topcoat layer can range from 1 to 6 mils (25 to 150 micrometers).
• a second substantially pigment free topcoat composition can be applied directly to the first topcoat layer to form a "clear-on-clear" topcoat.
• the first topcoat coating composition can be applied over the first base coating layer as described above.
• the second topcoat coating composition which may be the same or different from the first topcoat composition can be applied to a cured or to a dried first topcoat before the first basecoat layer and first topcoat layer have been cured.
• the first base coating layer, the first topcoat layer and the second topcoat layer can then be heated to cure the three coatings simultaneously.
• the base coating composition used to form the first base coating layer contains metallic or reflective pigments as are known in the art for use in color coats of the so-called color-plus-clear systems. These are the so-called “glamour finishes” whereby a differential light reflection effect, dependent upon the viewing angle, is achieved.
• This "flip-flop” effect can be attributed to the proper orientation (i.e., alignment parallel to the substrate surface) of the metallic and/or other reflective pigment in the base coating layer.
• Appearance properties such as gloss and distinctness of image, and smoothness, for the most part, can be attributed to the unpigmented topcoat (i.e., the clearcoat).
• the basecoat composition, which contains metallic and/or other reflective pigments is formulated to maximize the "flip-flop" effect; and the top coating composition, which is substantially pigment-free, is formulated to maximize appearance properties such as gloss.
• the above-described pigmented film-forming compositions are storage stable compositions which provide multi-layer composite coatings suitable for automotive color-plus-clear applications.
• the reflective pigment- containing base coats exhibit excellent "flip-flop” effect and excellent water resistance and appearance properties.
• the coating composition of the present invention when used as a metallic base coat composition, provides excellent metallic flake orientation as measured by Flop Index and include primarily HAPS compliant solvents. Further, the coatings derived from the present basecoat composition can be used with a wide variety of clearcoat chemistries and are able to maintain good metallic appearance by minimizing soak in or strike in. Also the coating compositions exhibit improved blistering resistance and interlayer adhesion properities.
• the multilayer composite coatings of the present invention can comprise two or more transparent topcoats applied over the base coat layer.
• the second transparent topcoat and the first transparent topcoat coating compositions can be the same or different provided that, when applied wet-on-wet, one topcoat does not substantially interfere with the curing of the other for example by inhibiting solvent/water evaporation from a lower layer.
• the first topcoat, the second topcoat or both can be the coating composition of the present invention. Alternatively, only one of the first topcoat and the second topcoat is formed from the curable coating composition of the present invention.
• the topcoat that does not comprise the coating composition of the present invention can include any of the art recognized crosslinkable coating compositions comprising at least one coating material and at least one curing agent.
• the coating compositions of the present invention can be advantageously formulated as a "monocoat", that is, a coating which forms essentially one coating layer when applied to a substrate.
• the monocoat coating composition can be pigmented.
• suitable pigments can include any of those mentioned above.
• the coating compositions of the present invention can be applied (by any of the conventional application techniques discussed above) in two or more successive coats, and, in certain instances can be applied with only an ambient flash period between coats.
• the multi-coats when cured can form essentially one coating layer.
• the coating composition described above can be present as a resinous phase dispersed in an aqueous phase.
• the coating composition can be used in a method of electrocoating a conductive substrate.
• this method of electrocoating a conductive substrate serves as an electrode in an electrical circuit comprising an electrode and a counter electrode, the substrate being immersed in the composition thermosetting.
• the method includes passing electric current between the cathode and the anode to cause deposition of the electrocoating composition on the substrate as a substantially continuous film.
• the present invention is also directed to a substrate coated using the above- described method.
• the first reactant having reactive functional groups and/or the curing agent may additional include an ionic or salt group.
• the ionic group may be cationic or anionic.
• the ionic group may be, for example, one or more of amine salts, quaternary ammonium and quaternary sulfonium groups.
• the cationic salt group may be derived from an epoxy group- containing monomer which after polymerization has been post-reacted with an amine salt or an amine and acid.
• Butyl ether of propylene glycol 2241.7 A dimerdiacid available from Cognis.
• the polyester polymer was prepared in a four-neck round bottom flask equipped with a thermometer, mechanical stirrer, condenser, dry nitrogen sparge and a heating mantle. The first four ingredients were heated to a temperature of 180°C and stirred in the flask until 257 grams of distillate was collected and the acid value dropped to the range of 22-25. The material was then cooled to a temperature of 130°C and the butyl ether of propylene glycol was added.
• the final product was a liquid having Gardner-Holdt viscosity of Z5- Z6, a non-volatile content of 71.1 % (as measured at 110°C for one hour), and a weight average molecular weight of 23,125 as measured by gel permeation chromatography using polystyrene standards.
• This example describes the preparation of an aqueous polyurethane dispersion containing polyurethane acrylate particles dispersed in an aqueous medium of the present invention.
• a latex containing a hydrophilic polyurethane prepolymer was prepared by adding 313.3g of N-methyl pyrrolidine; 234.4 g of hydroxyethyl methacrylate; 241.5 g of dimethylol proprionic acid; 2.3g of 2,6-Di-tert-butyl A- methyl phenol; 2.3g of triphenyl phosphate; and 2.3g of dibutyl tin dilaurate to a four necked round bottom flask fitted with a thermocouple, mechanical stirrer, and condenser and heated to 100°C in to obtain a homogeneous solution.
• compositions for this prepolymer is 25% diol (second surfactant-like prepolymer), 25% diacrylate (hydrophobic prepolymer), and 50% monofunctional in hydroxyl and acrylate (second surfactant-like prepolymer).
• Nonionic surfactant 70% in water, available from RHODIA, Paris, France.
• Biocide containing 9.3% 1 ,2-8enzisothiazolin-3-one as active Ingredient, available from Syngenta Corporation, Wilmington, DE.
• the following example describes the preparation of a latex emulsion containing crosslinked polymeric microparticles of the present invention.
• the aqueous dispersion was prepared as described below from the following ingredients. Amounts listed below indicate parts by weight (grams) unless otherwise noted.
• Anionic surfactant available as AOT-75 from Cytec Industries, Inc. 5 Anionic surfactant, available as Alipal CO-436 from GAF. 6 Proxel GXL from Avecia Chemicals. [000109] Charge 1 was added to a reactor fitted with thermocouple, agitator, and reflux condenser. The contents of the reactor were heated to a temperature of 83 0 C at which time Feed A was added over a one (1 ) minute period, followed by a hold period of two (2) minutes. Feed B was then added over a one (1 ) minute period and the contents of the flask were held at a temperature of 83°C for a period of 10 minutes. Feed C was then added over a 120-minute period.
• Feed D was added over a 120-minute period.
• the reaction mixture was held at a temperature of 83°C for 60 minutes, followed by cooling of the reaction product to ambient temperature.
• Feed E was then added.
• the final product was 30% solids by weight (as measured at 110 0 C for one hour) and had a particle size of 0.1 micron (as measured using a Horiba LA-900 Laser Scattering Particle Size Distribution Analyzer, available from Horiba Instruments, Irvine, California).
• Example 1 Two silver waterborne basec ⁇ at coating samples (Sample 1 and Sample 2) were prepared using the. components listed in Table 1 below. Weights of all components are listed in grams.
• the "Premix Portion” was first - prepared with all materials added under agitation in the order listed in Table 1. Then the "Basecoat Portion” was prepared using the "Premix Portion” at the amounts indicated by Table 1. Sample 1 was prepared without the polymer of Example D. Sample 2 was prepared with the polymer of Example D.
• LUBRIZOL 2062 A 60 / 36 / 4 w/w solution of LUBRIZOL 2062/diisopropanolamine/propylene glycol butyl ether.
• LUBRIZOL 2062 is available from the Lubrizol Co., Cleveland, OH.
• Example 3 Two mica-containing silver waterborne basecoat coating samples (Sample 3 and Sample 4) were prepared using the components listed in Table 2 below. All components are listed in grams. The "Premix Portion” was first prepared with all materials added under agitation in the order listed in Table 2. Then the “Basecoat Portion” was prepared using the "Premix Portion” at the amounts indicated by Table 2. Sample 3 was prepared without the polymer of Example D. Sample 4 was prepared with the polymer of Example D.
• Pigment paste of a 5,86:10.13 w/w ratio of Stapa Metallux 2154 and Stapa Metallux R 875 13 lriodim ' 9505 Red Violet . ' 1ft A 60/36/4 w/w solution of LUBRIZOL 2062/di.isopropanolamine/Propylene glycol Butyl . ether. LUBRIZOL 2062 is available from the Lubrizbl Co!, Cleveland, OH, . . .
• Samples 1 and 2 were each spray applied in a humidity and temperature controlled spray booth at 60% relative humidity ("RH") and 7O 0 F (21 0 C) onto cold rolled steel substrates which had been previously electrocoated with ED5000 and primed with 1177225A gray primer (both products available commercially from PPG Industries, Inc.), the primed panels having been prepared by ACT Laboratories Inc., of Hillsdale Ml.
• RH 60% relative humidity
• 7O 0 F 21 0 C
• 1177225A gray primer both products available commercially from PPG Industries, Inc.
• Each coating composition was spray-applied using the SATA LP90 gun with a MSB nozzle and 135 air cap.
• Samples 1 and 2 were spray applied such that the dry or cured film thickness of each coating was in the range of 0.4 to 0.6 mils (10.2 to 15.2 micrometers) thickness. These coated test panels were allowed an ambient air flash period of 3 minutes at 70°F(21°C)/60%RH, followed by heating for 3 minutes at 176 0 F (8O 0 C) to further dehydrate the coating.
• a two-component clearcoat composition 74984/74985 (available from PPG Industries, Inc.) was mixed at a weight ratio of 3 to 1 and spray applied over the panels coated with Samples 1 and 2. This clearcoat was spray applied such that between 1.4 and 1.6 mils (35.6 to 40.6 micrometers) of dry clearcoat film thickness was achieved.
• Samples 1 and 2 were re-applied to each of their respective coated panels. In other words, if the panel was originally coated with Sample 1 , Sample 1 was re-applied to that same panel. Both Samples 1 and 2 were sprayed so that the dry or cured film thickness was in the range of 0.4 to 0.6 mils (10.2 to 15.2 micrometers) thickness.
• Samples 3 and 4 were each spray applied in a humidity and temperature controlled spray booth at 60% relative humidity ("RH") and 7O 0 F (21 0 C) onto cold rolled steel substrates which had been previously electrocoated with ED5000 and primed with 1177225A gray primer (both products available commercially from PPG Industries, Inc.), the primed panels having been prepared by ACT Laboratories Inc., of Hillsdale Ml.
• RH 60% relative humidity
• 7O 0 F 21 0 C
• 1177225A gray primer both products available commercially from PPG Industries, Inc.
• Each coating composition was spray-applied using the SATA LP90 gun with a MSB nozzle and 135 air cap.
• Samples 3 and 4 were spray applied such that the dry or cured film thickness of each coating was in the range of 0.4 to 0.6 mils (10.2 to 15.2 micrometers) thickness. These coated test panels were allowed an ambient air flash period of 3 minutes at 70°F(21°C)/60%RH, followed by heating for 3 minutes at 176 0 F (8O 0 C) to further dehydrate the coating. [000124] After dehydration, a one-component clearcoat composition High Teck 97060 (available from PPG Industries, Inc.) was spray applied over the panels coated with Samples 3 and 4. This clearcoat was spray applied such that between 1.4 and 1.6 mils (35.6 to 40.6 micrometers) of dry clearcoat film thickness was achieved.
• High Teck 97060 available from PPG Industries, Inc.
• the coated test panels were allowed an ambient air flash of 10 minutes at 70°F(21°C)/60%RH, followed by heating for 30 minutes, at 285 0 F (14O 0 C)- All panels were allowed to cure at ambient conditions (70°F(21°C)/60%RH) for an additional 72 hours before testing. . .
• Panels coated with Samples 1 and 2 were tested in humidity and evaluated for blistering.
• Panels coated with Samples 3 and 4 were tested in humidity and watersoak and evaluated for blistering and adhesion as described below.
• Water soak test is a water immersion test. Coated panels are immersed in 63 0 C water for
• Adhesion was performed according to ASTM D3359! The higher the number, the better th ⁇ adhesion.

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